1,4-bis-(tris-(nf2)methoxy)-2,3-dinitroxybutane

ABSTRACT

1. The compound 1,4-bis-(tris-(NF2)methoxy) -2,3-dinitroxybutane having the compositional formula:

United States Patent [191 Stogryn et al.

{ ]March 20, 1973 1,4-BIS-[TRIS-(NF2)METHOXY]-2,3-

- DINITROXYBUTANE Inventors: Eugene L. Stogryn, Fords; Joel G. Berger, Elizabeth, both of N.J.; David S. Bosniack, New York, N.Y.

Assignee: Esso Research and Engineering Company Filed: Sept. 3, 1964 App1.No.: 395,110

US. Cl. ..260/467, 149/19, 149/22,

149/76, 149/88, 260/584 C Int. Cl ..C07c 77/02 Field of Search ..260/584 C, 467

Primary Examiner-Leland A. Sebastian Attorney-Welan, Chasan, Litton, Marx and Wright and Henry Berk EXEMPLARY CLAIM 1. The compound l,4-bis-[tris-(NF )methoxy]-2,3- dinitroxybutane having the compositional formula:

(NF COCH CH(ONO CH(ONO )CH OC(NF 6 Claims, No Drawings l,4-BIS-[TRlS-(NF2)METHOXY]-2,3- with perfluoroguanidine in an adductive reaction and DINITROXYBUTANE the resulting adduct is fluorinated. The synthetic route This invention relates to new high energy oxidizers i given as f ll N r, NF, N F,

I n m l I: NF: F,

that combine the energetic advantages of difluoramino This preparation is described in application Ser. No. and nitrato groups in isomeric compounds formed by 386,088 filed by E. L Stogryn et al. on July 29, 1964, the nitration of cis and trans isomers of 1,4-bis-[trisnow U.S. Pat. No. 3,564,023. (NFQmethoxyl-Z-butene oxide, which is given the ab- In making the cis-FABDE, the cis isomer of 1,4- breviated name FABDE. These isomeric compounds dihydroxy-Z-butene oxide is prepared by epoxidation containing the nitroxy or nitrato (-ONO groups of commercially available cis-1,4-dihydroxy-2-butene. linked to the carbon atoms which in the parent com- This isomer is used as reactant I to be reacted with the pound are in the oxide ring linkage are nonvolatile. perfluoroguanidine in acetonitrile with urea present as One of the isomers, the threo isomer, is a liquid; and catalyst. The reaction is stirred at room temperature the other which is the meso or erythro isomer is a solid. overnight and after removal of unreacted gases the In Particular, the new isomeric nitrates 0f FABDE solution is treated with a stream of mixed fluorine and prepared in accordance with the present invention are nitrogen gas f several h s t fl i te th add t the threo, and 'y isomersof z product III. The temperature of reaction for the t yly which is represented fluorination is low, e.g., -25C. To recover the cisy the following compositional formulw FABDE product in the acetonitrile is stripped off leav in a viscous residue which is dissolved in halogenated (NFDSCOCHZCH(ONO2)CH(ONO2)CH2OC(NF2)3 hy drocarbon, e.g., Freon 113 or CCl, and dried with An abbreviated name for this dinitrate of FABDE is anhydrous Na CO Th i d l i i filtered d FABDE'DN- These FABDE'DN compounds have been the solvent blown off. Then the residue is placed on a determined to have a number of important Propcrties silica gel column for chromatographic purification. which make m useful solid racket propellant The preparation of the trans-FABDE is carried out in mulatiohsare readily made in good Yields and 40 the similar manner as the preparation of the cishigh purity. The have suitable stability and compati- FABDE isomer starting with t J 4 dihydroxy 2 bubimy f l m i for producing f Propel tene oxide as the reactant l which is obtained by the '3 composftes other energy F caustic treatment of commercially available trans-1,4-

The sun-mfg compounds the synthejsm of the dichloro-2-butene followed by epoxidation. FABPE-QN isomers are the cis and trans isomers of The three and m- EWFABDBDN 14'bls'[ms'(NFz)methoxyl'z'butene oxlde' The as pounds are made in high yields by reaction of nitric 3:33: j g fgig g g g i react}? acid with the cis and trans-FABDE compounds respecor a s1 er 0 l y roxyu ene on e tivey asshown below.

TABLE I FABDE Product Product composition ONO: III Cis Thrco-FABDE-dinitrate-.... :)aC 0 :$-C CHIC C (NFa):

Trans ErythroFABDE-dinitrate. (NF2)a 0 HiC--C CHzCO (NFz):

NO: NO:

II CHzOC(NF2)z II CH;OC(NF,)

H ClIqOCUIFz); (NF:)zCOCH H ONOa ONOz Three-FABDE-DN. Meso or erythro-FABDE-DN.

Either of the FABDE isomers is reacted with 98% l-lNO in methylene chloride or other inert diluents at ambient or refluxing temperatures. After the reaction, the products are purified to the desired extent for the recovery of a final purified product illustrated in the following examples.

EXAMPLE 1 Synthesis of threo-l,4-bis-{tris-(NF )methoxy]-2,3- dinitroxybutane To a solution of 1.0 g. of cis-FABDE in ml. of cH Cl was added 4 ml. of 98% l-lNO; in 2 ml. of CH Cl After refluxing for four hours the cooled reaction mixture was poured into ice-water. The methylene chloride solution was washed with water, a dilute sodium carbonate solution, and dried over M gSO A capillary G.C. of the crude reaction mixture showed it was a mixture of dinitrate and mono-nitrate in a ratio of 75/25, respectively.

The nitrate was purified by column chromatography on base treated silica gel (20 times the weight of the adduct). Elution with CC1 gave pure threo-FABDE dinitrate in 67 percent yield. The dinitrate is a colorless viscous oil.

Chloroform displaced the mono-nitrate from the column. After recrystallization from pentane the mono-nitrate melted at 40C.

The dinitrate product was analyzed and found by elemental analysis to have a composition in agreement with the calculated analysis for c l-l N o F and infrared and N.M.R. analysis to have the following structure:

Synthesis of erythro-l,4-bis-[tris-(NF )methoxy]-2,3- dinitroxybutane A solution of trans-FABDE (4.2 g.) in 70 mls. of CH Cl was treated with 14 mls. of 98% l-lNO and the mixture allowed to stir at ambient temperature for 2% days. At the end of this time, the excess HNO was removed by several water washes, and the Cl-l cl solution dried. Removal of solvent gave 3.9 g. of crude oily product, which was chromatographed on silica gel using CHCl as the eluent. Purity of the eluted material was monitored by use of thin layer chromatography (silica gel layer). Cuts which showed only one spot were dissolved in pentane and recrystallized several times from this solvent to yield solid dinitrate m.p. 35 to 37C.

The dinitrate product was identified by an elemental analysis to have the composition calculated for C l-l bi 0 F and by N.M.R. and infrared analysis to have the structure shown below:

Significant properties and a comparison of property differences between the FABDE-DN isomers are listed as follows:

A. The erythro isomer, which is solid, has the higher melting point.

B. The erythro isomer is less sensitive.

C. Both isomers have similar high stabilities, DTA and VTS. DTA, the differential thermal analysis exotherm temperature, is a measure of stability to decomposition and heated to the temperatures set forth. VTS is the measure of gaseous decomposition under controlled time and temperature for the purpose of determining thermal stability.

A number of solid rocket formulations have been made with the FABDE-DN isomers and it was found that they can be used advantageously with energetic polymers or with nonenergetic polymers in the binders. The liquid threo-isomer acts as a suitable plasticizer with solid partially hydrolyzed polyvinyl alcohol-trityl triisocyanate which is shown to be a highly useful nonenergetic binder polymer in application Ser. No. 396,479 filed by A. H. Muenker et al. on Sept. ll, 1964.

Compositions of 288+ lsp level containing the threo- FABDE-DN have been formulated and tested for burning'rates. The physical properties of the solid racket propellant grains made with this dinitrate plasticizer used in high proportion to the polymer were found to be satisfactory. Characteristics of two compositions formulated are given in the following table.

TABLE II Cure Conditions: 5 days at room temperature HPVA Polyvinyl acetate alcohol, hydrolysis 24.9

Theor. P

Tensile Strength Composition Elongation 43.2% Binder (5/l Dinitrate IHPVA) 42.5% Solid Poly FABDE 12.7% Ammonium Perchlorate 1.6% Boron Powder Tris Compounds: 78.5% 45% Binder (8/1 Dinitrate IHPVA) 42% Poly FABDE 10.5% Ammonium Perchlorate 2.5% Boron Powder Tris Compounds: 82.3%

2. The compound threo-l,4-bis-[tris-(NF,)methoxy]-2,3- dinitroxybutane having the compositional formula:

3. The compound erythro-l,4-bis-[tris-(NF )methoxy]-2,3-dinitroxybutane having the compositional formula:

4. Process for preparing 1,4-bis-[tris-(NF,)methoxy]-2,3-dinitroxybutane which comprises reacting 1,4- bis-[tris-(NF )methoxy]-2-butene oxide with nitric acid to form the compound 1,4-bis-[tris-(NFQmethoxy]-2,3-dinitroxybutane as product, and recovering said product.

6. In the process of claim 4, reacting the trans isomer of l,4-bis-[tris-(NF )methoxy]-2-butene oxide with nitric acid to form erythro-l,4-bis-[tris-(NF )methoxy]-2,3-di nitroxybutane as product, and recovering said product. 

1. THE COMPOUND 1,4-BIS- TRIS-(NF2)METHOXY!-2,3-DINITROXYBUTANE HAVING THE COMPOSITIONAL FORMULA: (NF2)3COCH2CH(ONO2)CH(ONO2)CH2OC(NF2)3.
 2. The compound threo-1,4-bis-(tris-(NF2)methoxy)-2,3-dinitroxybutane having the compositional formula:
 3. The compound erythro-1,4-bis-(tris-(NF2)methoxy)-2,3-dinitroxybutane having the compositional formula:
 4. Process for preparing 1,4-bis-(tris-(NF2)methoxy)-2,3-dinitroxybutane which comprises reacting 1,4-bis-(tris-(NF2)methoxy)-2-butene oxide with nitric acid to form the compound 1,4-bis-(tris-(NF2)methoxy)-2,3-dinitroxybutane as product, and recovering said product.
 5. In the process of claim 4, reacting the cis isomer of 1,4-bis(tris-(NF2)methoxy)-2-butene oxide with nitric acid to form the threo-1,4-bis-(tris-(NF2)methoxy)-2,3-dinitroxybutane as product, and recovering said product.
 6. In the process of claim 4, reacting the trans isomer of 1,4-bis-(tris-(NF2)methoxy)-2-butene oxide with nitric acid to form erythro-1,4-bis-(tris-(NF2)methoxy)-2,3-dinitroxybutane as product, and recovering said product. 